Surface composition analysis by low-energy ion scattering

Low-energy ion scattering (LEIS) is an analytical tool that provides information on the atomic composition of the outer surface, when noble gas ions are used as projectiles. In fact, quantitative composition analysis is currently done on a huge variety of materials, including catalysts and organic materials. The information on the surface composition is contained in the signal of backscattered ions (typically 1–3 keV He⁺,Ne⁺). In order to translate the LEIS signal to an elemental surface concentration all factors determining the LEIS signal must be known. These are in particular the scattering cross section and the ion fraction of the backscattered particles. The scattering cross section, which is due to the screened electrostatic potential between target atom and projectile, is well-known for the prevailing conditions of LEIS. It is an intriguing fact that, despite the large quantity of successful applications, the charge exchange processes in LEIS are not yet fully understood. It is e.g. not known why in LEIS for a given atomic species on the surface the signal usually does not depend on which other species are present (absence of matrix effects). Significant progress has recently been made in the understanding of the underlying charge exchange processes.Therefore, the aim of this review is twofold: on the one hand, to summarize the present understanding of the factors that determine the ion fraction of the scattered projectiles in LEIS, i.e. charge exchange processes. On the other hand, to summarize how quantitative surface composition analysis can be accomplished.In addition, we critically review publications that deal with surface composition analysis by LEIS, and analyze in which cases and by what means this was achieved and where and why it was successful or failed. After reading this review the reader will be able to deal with the pitfalls encountered in LEIS and to choose preferred experimental conditions for quantitative surface composition analysis.     

LEED structure determination of the Ni(1 1 1)(√3×√3)R30°-Sn surface

Quantitative low energy electron diffraction has been used to determine the structure of the Ni(1 1 1)(√3×√3)R30°-Sn surface phase. The results confirm that the surface layer comprises a substitutional alloy of composition Ni₂Sn as previously found by low energy ion scattering (LEIS), and also shows that there is no stacking fault at the substrate/alloy interface as has been found in (√3×√3)R30°-Sb surface alloys on Ag and Cu(1 1 1). The surface alloy layer is rumpled with the Sn atoms 0.45 ± 0.03 Å higher above the substrate than the surrounding Ni atoms. This rumpling amplitude is almost identical to that previously reported on the basis of the LEIS study. Comparison with similar results for Sn-induced surface alloy phases on Ni(1 0 0) and Ni(1 1 0) shows a clear trend to reduced rumpling with reduced surface atomic layer density, an effect which can be rationalised in terms of the different effects of valence electron charge smoothing at the surface.     

Investigation of oxygen adsorption on Cu(110) by low-energy ion bombardment

The interaction of molecular oxygen with a Cu(110) surface is investigated by means of low energy ion scattering (LEIS) and secondary ion emission. The position of chemisorbed oxygen relative to the matrix atoms of the Cu(110) surface could be determined using a shadow cone model, from measurements of Ne⁺ ions scattered by adsorbed oxygen atoms. The adsorbed oxygen atoms are situated 0.6 ± 0.1 Å below the midpoint between two adjacent atoms in a 〈100〉 surface row. The results of the measurements of the ion impact desorption of adsorbed oxygen suggest a dominating contribution of sputtering processes. Ion focussing effects also contributes to the oxygen desorption. The ion induced and the spontaneous oxygen adsorption processes are studied using different experimental methods. Sticking probability values obtained during ion bombardment show a strong increase due to the ion bombardment.     

Influence of ion bombardment induced radiation damages in the crystal lattice on the angular regularlties in ion scattering

The paper examines the angular, spatial and energy distribution of ions scattered by various faces of silicon and germanium single crystals. It is shown that, due to the orderly arrangement of atoms in the crystal lattice, the orientation effects in the angular, spatial and energy distributions are observed at temperatures exceeding the annealing temperature of ion bombardment induced radiation damage. At high temperatures of the sample a reduction of the anisotropy in the angular, spatial and energy distributions of scattered ions was observed which is due to the changing transparency of the crystal resulting from the thermal vibrations of atoms in the lattice.

Results of investigations testify to the possibility of using the orientation dependences of phenomena occurring during the interaction of ions with crystals for determining the annealing temperature of ion bombardment damage and for studying the kinetics of the process of ion bombardment. It is shown that further studies along the same lines as conducted by the authors of this paper could develop a technique for the quantitative estimation of ion bombardment damage in crystals and also in thin epitaxial films.     

Structure of ultra-thin Ti film on the Al(001) surface

The atomic structure of sub-monolayer amounts of Ti deposited on the Al(001) surface at room temperature has been investigated using low-energy electron diffraction (LEED) and low-energy ion scattering spectroscopy (LEIS). The Ti coverage was determined using Rutherford backscattering spectroscopy (RBS). Though a crisp LEED image is inherently difficult to obtain, the symmetry of the observed c(2 × 2) LEED images allows us to infer a structure which places Ti atoms in every other Al lattice site. Analysis of the LEIS azimuth- and polar-angle scan spectra has been done to determine the best structural model which supports the c(2 × 2) symmetry of the LEED image as well as LEIS experimental data. It was concluded that the best model consistent with the experimental data, puts Ti preferentially below the surface of the Al substrate at every other lattice site for sub-monolayer coverage of Ti on Al(001). As Ti coverage increases, the presence if Ti atoms in the surface layer also increases. Results of this study are relevant to research pertaining to the possible use of Ti as a catalyst in sodium alanate (NaAlH₄) in hydrogen storage applications.     

Sputter damage in Si surface by low energy Ar+ ion bombardment

The damage distributions in Si(1 0 0) surface after 1.0 and 0.5 keV Ar⁺ ion bombardment were studied using MEIS and Molecular dynamic (MD) simulation. The primary Ar⁺ ion beam direction was varied from surface normal to glancing angle. The MEIS results show that the damage thickness in 1.0 keV Ar ion bombardment is reduced from about 7.7 nm at surface normal incidence to 1.3 nm at the incident angle of 80°. However, the damage thickness in 0.5 keV Ar ion bombardment is reduced from 5.1 nm at surface normal incidence to 0.5 nm at the incident angle of 80°. The maximum atomic concentration of implanted Ar atoms after 1 keV ion bombardment is about 10.5 at% at the depth of 2.5 nm at surface normal incidence and about 2.0 at% at the depth of 1.2 nm at the incident angle of 80°. However, after 0.5 keV ion bombardments, it is 8.0 at% at the depth of 2.0 nm for surface normal incidence and the in-depth Ar distribution cannot be observable at the incident angle of 80°. MD simulation reproduced the damage distribution quantitatively.     

Surface hydrogen detection by low energy He ion scattering spectroscopy

Hydrogen adsorbed on a Si(100) surface can be detected by angle-resolved LEIS (low-energy ion scattering spectroscopy) which uses a ⁴He⁺ ion beam with incident energies around 1 keV. The scattering peaks from the surface hydrogen are restricted to narrow scattering angles from 0° to 15°, which is in agreement with those expected by the binary elastic collision model.     

Oxygen induced segregation of aluminum to α-Cu-Al(1 0 0) alloy surfaces studied by low energy ion scattering and X-ray photoelectron spectroscopy

The effect of annealing temperature on the surface composition of α-Cu-Al(1 0 0) alloys for aluminum concentrations of 5, 12 and 17 at% was investigated using X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Two initial states of the sample surfaces were examined: sputter-cleaned and oxidized. The effect of annealing temperature on segregation is different for sputter-cleaned and oxidized samples. Aluminum preferential sputtering and strong oxygen induced aluminum segregation were detected on all examined samples. Whilst for the sputter-cleaned surfaces a small thermal induced segregation was observed, the combination of annealing and oxygen exposure resulted in aluminum enrichment in the 100-300% range relative to the bulk concentration. The segregation rate is proportional to the aluminum concentration for sputter-cleaned surfaces and displays a maximum for the oxidized α-Cu-Al(12 at.%)(1 0 0) surface.     

Influence of surface topography on the secondary electron yield of clean copper samples

Secondary electron yield (SEY) due to electron impact depends strongly on surface topography. The SEY of copper samples after Ar-ion bombardment is measured in situ in a multifunctional ultrahigh vacuum system. Increasing the ion energy or duration of ion bombardment can even enlarge the SEY, though it is relatively low under moderate bombardment intensity. The results obtained with scanning electron microscopy and atomic force microscopy images demonstrate that many valley structures of original sample surfaces can be smoothed due to ion bombardment, but more hill structures are generated with stronger bombardment intensity. With increasing the surface roughness in the observed range, the maximum SEY decreases from 1.2 to 1.07 at a surface characterized by valleys, while it again increases to 1.33 at a surface spread with hills. This phenomenon indicates that hill and valley structures are respectively effective in increasing and decreasing the SEY. These obtained results thus provide a comprehensive insight into the surface topography influence on the secondary electron emission characteristics in scanning electron microscopy.     

Relaxation of the edge atoms of a stepped Cu(410) surface

The edge atom position of the stepped Cu(410) surface has been investigated with low energy ion scattering (LEIS) using 10–20 keV H⁺. It is possible to determine the atomic position by utilizing atomic shadowing effects. The scattered particles are analysed with a time-of-flight spectrometer. This means that we can detect scattered hydrogen leaving the copper surface in the neutral state as well as in the charged state, so the influence of neutralization of the scattered particles along different outgoing trajectories is eliminated. We find an inward relaxation of the edge atoms; assuming that this relaxation takes place in the (100) plane it amounts to about 8% of the interlayer spacing.     

Structural and electrical analysis of S ion bombarded p-InP(1 0 0)

The chemical state of sulfur and surface structure on low-energy S⁺ ion-treated p-InP(1 0 0) surface have been investigated by high-resolution X-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED). S⁺ ion energy over the range of 10-100 eV was used to study the effect of ion energy on surface damage and the process of sulfur passivation on p-InP(1 0 0) by S⁺ ion beam bombardment. It was found that sulfur species formed on the S⁺ ion-treated surface. The S⁺ ions with energy above 50 eV were more effective in formation of In-S species, which assisted the InP surface in reconstruction into an ordered (1 × 1) structure upon annealing. After taking into account physical damage due to the process of ion bombardment, we found that 50 eV was the optimal ion energy to form In-S species in the sulfur passivation of p-InP(1 0 0). The subsequent annealing process removed donor states that were introduced during the ion bombardment of p-InP(1 0 0). Results of theoretical simulations by Transport of Ions in Materials (TRIM) are in accordance with those of experiments.     

Low sputter damage of metal single crystalline surfaces investigated with medium energy ion scattering spectroscopy

It was observed clearly that the sputter damage due to Ar⁺ ion bombardment on metal single crystalline surfaces is extremely low and the local surface atomic structure is preserved, which is totally different from semiconductor single crystalline surfaces. Medium energy ion scattering spectroscopy (MEIS) shows that there is little irradiation damage on the metal single crystalline surfaces such as Pt(111), Pt(100), and Cu(111), in contrast to the semiconductor Si(100) surfaces, for the ion energy of 3–7 keV even above 10¹⁶–10¹⁷ ions/cm² ion doses at room temperature. However, low energy electron diffraction (LEED) spots became blurred after bombardment. Transmission Electron Microscopy (TEM) studies of a Pt polycrystalline thin film showed formation of dislocations after sputtering. Complementary MEIS, LEED and TEM data show that on sputtered single-crystal metal surfaces, metal atoms recrystallize at room temperature after each ion impact. After repeated ion impacts, local defects accumulate to degrade long range orders.     

Argon (10 keV) scattered from structures,induced by bombarding a Cu(100) surface; ionization and neutralization

The ion fractions, η⁺, of 10 keV argon particles, scattered from a damaged copper surface, are measured with a time of flight spectrometer. The damage was introduced by bombardment with argon ions. The scattering angle was 30°. The results for different angles of incidence, ψ, are reported. For Ψ < 10° the ion fraction is relatively high (～27% for Ψ = 4°) and decreases as Ψ increases. For Ψ = 15° the value of η⁺ is 7%, whereas for 21° < Ψ < 27° the value of η⁺ appears to be constant (～14%). An explanation is given by assuming interatomic ionization as well as neutralization processes along the trajectory of the scattered particles. The number of step-atoms, induced by ion bombardment, is estimated to be about 2 × 10¹⁴/cm².     

Preferential sputtering of TIC under keV Ar+ ion bombardment: Simultaneous sputtering-ISS measurement with He+ and Ar+ ions

The composition change of the outermost atom layer of TiC(110) under ion bombardment with 1.5–3 keV He⁺ and He⁺ + Ar⁺ ions has been measured by ion scattering spectroscopy with He⁺ ions at different sample temperatures. It has been found that the preferential sputtering of C atoms takes place for both the He⁺ and Ar⁺ ion bombardment, however the preferred sputtering is more pronounced for Ar⁺ ions than for He⁺ ions. The ion bombardment with He⁺ ions at elevated sample temperatures hardly results in any change in surface composition below ～800°C, while Ar⁺ ion bombardment results in C enrichment for elevated temperatures as reported so far.     

Glancing-angle ion enhanced surface diffusion on gaAs(001) during molecular beam epitaxy

We describe the effects of glancing incidence 3-4 keV Ar ion bombardment on homoepitaxial growth on vicinal GaAs(001). The average adatom lifetime on surface terraces, measured during growth using specular ion scattering, decreased monotonically with increasing ion current density. The results indicated that surface diffusivity was increased by the ions. The ion beam also suppressed growth oscillations and decreased the film surface roughness. This indicates a change from two-dimensional island nucleation to step-flow growth due to increased adatom surface diffusivity. A simple model, involving direct momentum transfer from ions to adatoms, is shown to be consistent with the measured enhanced diffusion.     

Neutralization mechanisms in He-Al surface collisions

From a quantum mechanical calculation where the populations of He ground and first excited states are properly taken into account, we can identify for the first time the neutralization to the He first excited state as an operative mechanism in He⁺-Al surface collisions. This identification allows us to understand the presence of high energy electrons in the ion induced electron emission spectra, through the inclusion of Auger deexcitation as an electron emission source, as well as to suggest a possible cause for the disagreement still found between theory and experiments in low energy ion scattering (LEIS) for this system.     

Study of S ion-assisted sulfurization of n-GaAs (1 0 0) surface

The chemical structure and site location of sulfur atoms on n-GaAs (1 0 0) surface treated by bombardment of S⁺ ions over their energy range from 10 to 100 eV have been studied by X-ray photoelectron spectroscopy and low energy electron diffraction. The formation of Ga-S and As-S species on the S⁺ ion bombarded n-GaAs surface is observed. An apparent donor doping effect is observed for the n-GaAs by the 100 eV S⁺ ion bombardment. It is found that the S⁺ ions with higher energy are more effective in the formation of Ga-S species, which assists the n-GaAs (1 0 0) surface in reconstruction into an ordered (1 × 1) structure upon subsequent annealing. The treatment is further extended to repair Ar⁺ ion damaged n-GaAs (1 0 0) surface. It is found that after a n-GaAs (1 0 0) sample is damaged by 150 eV Ar⁺ ion bombardment, and followed by 50 eV S⁺ ion treatment and subsequent annealing process, finally an (1 × 1) ordering GaAs (1 0 0) surface with low surface states is obtained.     

Variation of the Crystal Structure on Si(111) Surface Induced by Ion Bombardment and Subsequent Annealing

Technical Physics - Modification of Si(111) surface due to ion bombardment and subsequent annealing has been studied. It has been found that annealing following bombardment with 0.3- to 1.0-keV...     

Resonant charge transfer in low-energy ion scattering: Information depth in the reionization regime

Time-Of-Flight Low-energy ion scattering (TOF-LEIS) experiments were performed for He(+) ions scattered from Cu(100) and Cu(0.5)Au(0.5)(100). Probabilities for resonant neutralization and reionization in close collisions were deduced in a wide energy range. To learn about the information depth in LEIS, in a next step ion spectra were analyzed for polycrystalline Cu samples. The relative yield of backscattered projectiles, which have undergone distinct charge exchange processes, was calculated. Results indicate a strong contribution to the ion yield that origins from particles reionized in a close collision in deeper layers when experiments are performed at energies where reionization is prominent. The surface sensitivity of the ion signal at different energies is quantified. Based on these results, the total ion spectrum was quantitatively modelled by two consistent, but different approaches.     

Vacancy-type defect distributions near argon sputtered Al(100) surface studied by variable-energy positrons and molecular dynamics simulations

A beam of variable-energy positrons, whose back-diffusion probability is measured as a function of positron implantation energy, is applied to studies of depth distribution of sputtering damage in aluminum. The defects are produced by argon ion bombardment of an Al(110) surface in ultra-high vacuum. We have varied the Ar⁺ energy, incident angle and dose, as well as sputtering and annealing temperatures. The extracted defect profiles have typically a narrow peak at the surface with a width of 10–20 A and a broader tail extending down to 50–100 Å. The shape of the defect profile varies only slightly with the sputtering energy and angle. Defect production at less than 1 keV Ar⁺ energies is typically 1–5 vacancies per incident ion. The defect profiles become fluence-independent at about 2 × 10¹⁶ Ar⁺ cm⁻². The defect density at the outer atomic layers saturates at high argon fluences to a few at%, depending on sputtering conditions. The sputtering temperature (below or above the vacancy migration stage at 250 K) has little effect on vacancy profiles. Defects anneal out gradually between 100 °C and 400 °C. Sputtering damage was also evaluated with the molecular dynamics technique. The shape and depth scale of the simulated collision cascades are in agreement with the experimentally extracted quantities.